Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/14—Nitrogen-containing compounds

Definitions

• the invention relates to methods and compositions for inhibiting corro- sion of metals, and, in one aspect, more particularly relates to methods and compositions for inhibiting corrosion of metals in acid environments where the acid contains halogen, such as hydrochloric acid, hydrofluoric acid, and the like.
• the vast majority of production and workover conduits comprised carbon steels. These steels were utilized either temporarily or permanently in the well, and treatment and/or stim- ulation fluids were introduced through them into the well.
• the production and workover conduits for use in the wells have been made of high alloy steels.
• the high alloy steels include chrome steels, duplex steels, stainless steels, martensitic alloy steels, ferritic alloy steels, austenitic stainless steels, precipitation-hardened stainless steels, high nickel content steels, and the like.
• R is a radical selected from the group consisting of abietyl, hydroabietyl, and dehydroabietyl
• Y is the group CH 2 R 1
• X is a radical selected from the group consisting of hydrogen and CH ⁇
• R t represents alpha ketonyl groups.
• U.S. Pat. No. 3,077,454 describes compositions for inhibiting corrosion made by combining certain active hydrogen containing compounds with organic ketones having at least one hydrogen atom on the carbon atom alpha to the carbonyl group and an aldehyde selected from the group consisting of aliphatic aldehydes containing from 1 to 16 carbons, and aromatic aldehydes of the benzene series, having no functional groups other than aldehyde groups, and a fatty acid.
• Still another object of the invention is to provide a halogen acid corrosion inhibitor that has improved performance as compared with conventional corrosion inhibitors.
• a corrosion inhibitor having at least one corrosion inhibitor base selected from the group consisting of Mannich reaction products and nitrogen-substituted heterocycles of 6 to 10 members quaternized with at least one alkyl or aryl halide, and at least one first solvent selected from the group consisting of Ci acids and ester derivatives thereof and salts thereof. At least one surfactant may be optionally present. An additional, second solvent may also be optionally present.
• the invention also concerns methods of inhibiting the corrosion of metals in the presence of liquids containing at least one halogen acid and the corrosion inhibitor of this invention.
• the corrosion of the metal is inhibited as compared with a liquid otherwise identical but absent the corrosion inhibitor of this invention.
• the invention includes fluids for contacting metal surfaces that have had their corrosion inhibition improved by the corrosion inhibitor of this invention.
• the single Figure is a chart comparing the corrosion loss in lbs/ft 2 (kg/m 2 ) for a corrosion inhibitor of this invention with a conventional corrosion inhibitor as a function of temperature.
• useful halogen acid corrosion inhibitor may be provided by the use of at least one corrosion inhibitor base selected from the group consisting a Mannich reaction product and a nitrogen-substituted heterocycle of 6 to 10 members quaternized with alkyl halides, at least one solvent, and optionally at least one surfactant.
• the solvent is a Ci acid or derivative thereof, particularly ester derivatives thereof.
• the Mannich reaction products may include, but are not necessarily limited to, the materials of U.S. Pat. Nos. 3,077,454; 5,366,643; and 5,591 ,381.
• the products of U.S. Pat. No. 3,077,454 can be made with approximately a 50% yield, and they require the presence of a fatty acid, such as a tall oil fatty acid, in one non-limiting embodiment.
• a fatty acid such as a tall oil fatty acid
• the nitrogen-substituted heterocycles of 6 to 10 members quaternized with alkyl halides are also commonly referred to as coal tar based quats. These materials are typically quinolines, pyridines and the like quaternized with alkyl and/or aryl halides, where the alkyl or aryl group may range from methyl to benzyl (Ci to C ⁇ ). Naphthyl quinoline quats are included in this group. Further information may be found with reference to U.S. Pat. No. 2,814,593, incorporated by reference herein, which discusses benzyl chloride quats of quinoline.
• the surfactant suitable for use in the method of this invention may be, in one non-limiting embodiment, an esterified alcohol that has been alkoxylated.
• the alkoxylation is achieved by reaction with ethylene oxide.
• Propylene oxide and butylene oxide may also be used, as well as combinations thereof, such as a combination of ethylene oxide and pro- pylene oxide.
• Suitable alcohols have from about 6 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and may have more than one hydroxyl group, in one non-limiting embodiment from 1 to 6 hydroxyl groups, and in another non-limiting embodiment from 1 to 3 hydroxyl groups.
• Particular alcohols expected to be useful in preparing the surfactants for the compositions of this invention include, but are not necessarily limited to, sorbitol, glycerol, ethylene glycol, alkylphenols, and mixtures thereof.
• the surfactant is made by esterifying sorbitol with one mole of tall oil and then reacting the product thereof with ethylene oxide until the desired properties are obtained.
• the desired properties include, but are not necessarily limited to, facilitating, improving and assisting the corrosion inhibitor base and the solvent in contacting any metal in contact with the fluid being inhibited.
• a suitable amount of ethylene oxide may range from about 3 to about 60 moles, preferably from about 12 to about 40 moles in another non-limiting embodiment of the invention, and from about 3 to about 30 mules in yet another non-limiting embodiment.
• formic acid will be the solvent of choice, although other materials are expected to function equivalently. These materials include, but are not necessarily limited to ester derivatives of C-i acids, and salts of these acids or ester derivatives.
• the solvent may include, but is not necessarily limited to, formate salts, methyl formate, ethyl formate, benzyl formate, formate salts of amines, inorganic formates and mixtures thereof.
• inventive solvents unexpectedly and surprisingly give better results than conventional solvents such as unmodified or unreacted alcohols, which in one embodiment of the invention are preferably absent.
• it may be desirable in some embodiments to use conventional solvents as a second solvent such as low carbon number alcohols, e.g.
• IPA isopropyl alcohol
• these conventional solvents may be optionally present in the corrosion inhibitor in proportions from about 0 to about 50 volume % in one non-limiting embodiment, and from 0 to about 30 volume % in an alternate non-limiting embodiment.
• the proportions of the various components in the corrosion inhibitor composition may range from about 10 to about 60 vol. % corrosion inhibitor base, from about 5 to about 50 vol. % surfactant, and from about 3 to about 50 vol. % solvent.
• the corrosion inhibitor composition may range from about 10 to about 50 vol. % corrosion inhibitor base, from about 10 to about 50 vol.
• the corrosion inhibitor includes about 20% to 40% corrosion inhibitor base, about 20% to 40% surfactant, and about 10% to 40% solvent.
• the halogen acid environments where the invention is useful encompass acid environments where the acid includes, but is not limited to, hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, and mixtures thereof.
• the composition of this invention has been found to have excellent stability, thus avoiding degradation over time. These corrosion inhibitors will be cost effective and provide excellent corrosion control.
• the acid corrosion inhibitor may be combined with any suitable acidic injection medium, including but not necessarily limited to, such media as down- hole acidizing fluids and compositions; 15% and 28% concentrations of HCI, 15-5% acetic acid/HCI blend. It aids corrosion control at elevated temperatures and pressures with the inventive inhibitor.
• acetylenic compounds such as acetylenic alcohols; cinnamaldehyde; a nitrogen compound, such as a quaternary ammonium compound; solvents such as alcohols or ketones; and aromatic hydrocarbons or mixtures thereof, as are known to those skilled in the art.
• any acetylenic compound such as acetylenic alcohols; cinnamaldehyde; a nitrogen compound, such as a quaternary ammonium compound; solvents such as alcohols or ketones; and aromatic hydrocarbons or mixtures thereof, as are known to those skilled in the art.
• teachings from acid corrosion inhibitors as made and described in U.S. Pat. Nos. 3,514,410; 3,404,094; 3,107,221 ; 2,993,863; and 3,382,179; may be utilized in accordance with the present invention. All of these patents are hereby incorporated by reference.
• the corrosion inhibitor contains at least one acetylenic alcohol having from 3 to 10 carbon
• acetylenic compounds examples include propargyl alcohol (2-propyn-1-ol), hexynol, dimethyl hexynol, diethyl hexynediol, dimethyl hexynediol, ethyl octynol, dimethyl octynediol, methyl butynol, methyl pentynol, ethynyl cyclohexynol, 2-ethyl hexynol, phenyl butynol, and ditertiary acetylenic glycol.
• propargyl alcohol (2-propyn-1-ol
• hexynol dimethyl hexynol
• diethyl hexynediol dimethyl hexynediol
• ethyl octynol dimethyl octy
• acetylenic compounds which can be employed in accordance with the present invention include, but are not limited to, butynediol; 1-ethynylcyclo- hexanol; 3-methyl-1-nonyn-3-ol; 2-methyl-3-butyn-2-ol; also 1-propyn-3-ol; 1- butyn-3-ol; 1-pentyn-3-ol; 1-heptyn-3-ol; 1-octyn-3-ol; 1-nonyn-3-ol; 1-decyn-3- ol; 1-(2,4,6-trimethyl-3-cyclohexenyl)-3-propyne-1-ol; and in general acetylenic compounds having the general formula: R 1
• R 3 wherein R 1 is -H, -OH, or an alkyl radical; R 2 is -H, or an alkyl, phenyl, substituted phenyl or hydroxyalkyl radical; and R 3 is -H or an alkyl, phenyl, substituted phenyl or hydroxyalkyl radical.
• the nitrogen or ammonia compounds that can be optionally employed in accordance with the present invention may include, but are not limited to, those amines having from 1 to 24 carbon atoms in each alkyl moiety as well as the six-membered heterocyclic amines, for example, alkyl pyridines, crude quinolines and mixtures thereof.
• alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety, such alkyl substituents having from one to 12 carbon atoms, and preferably those having an average of six carbon atoms per pyridine moiety, such as a mixture of high boiling tertiary-nitrogen-heterocyclic compounds, such as HAP (high alkyl pyridines), Reilly 10-20 base and alkyl pyridines H3.
• Other nitrogen compounds include the crude quinolines having a variety of substituents.
• the corrosion inhibitor may also contain a number of other constituents, such as fatty alcohol adducts, nonyl phenol adducts and tallow amine adducts, tall oil adducts, such as surfactants. Oil wetting components, such as heavy aromatic solvents, may also be present.
• the corrosion inhibitor contains at least one saturated alcohol having from 1 to 5 carbon atoms, and at least one alkyl phenol or alkoxylated alkyl phenol having from 15 to 24 carbon atoms.
• the corrosion inhibitor has an absence of a source of molybdate ions. In yet another non-limiting embodiment of the invention, the corrosion inhibitor has an absence of cinna- maldehyde or substituted cinnamaldehyde.
• the halogen acid corrosion inhibitor of this invention may be used with conventional corrosion inhibitors as described above and below, and in any application where a steel surface, such as stainless steel, high alloy or other steel, is exposed to an acid environment. While the specific implementation of this invention is described in the context of the oil patch, the invention may certainly find uses in other applications where it is desirable to reduce corrosion, such as chemical processes that necessarily require the contact of acids with conduits, fittings, and other equipment, such as industrial cleaning applications.
• a fluid is introduced through a high alloy steel member or conduit positioned within the well.
• the fluid is an acidic injection medium and includes an acid corrosion inhibitor.
• the invention also encompasses a method of treating a well for enhancement of production within a production zone by introduction into the steel conduit of the acid corrosion inhibitor composition of this invention.
• the fluid which is contemplated for use in one aspect of the present invention for treatment of a subterranean well for enhancement of production will be aqueous based; that is, it will be formed using sea water available at the well location, a brine, tap water or similar fluid.
• the amount of fluid used for the treatment will vary, of course, from well to well, and will be based upon the particular application at hand, and the amount thereof is not particularly critical to the method of the present invention. It will be appreciated that one of ordinary skill in the art of corrosion inhibition will be able to adapt the teachings of this invention to applications outside the realm of oil and gas recovery, such as the area of chemical processing, with only routine experimentation.
• the expected treatment fluid in an oil production environment is expected to have as a primary additive an acidic injection medium, which may be any compatible acid, including but not limited to hydrochloric acid, hydrofluoric acid, other mineral acids, other halogen acids, and mixtures thereof.
• the fluid with the acid injection medium therein should have a pH of no greater than about 6.9.
• Acidizing fluids can have pH of less than 1 when mixed with produced fluids which may have a pH as high as 6.9.
• the treatment fluid also contemplates incorporation of other acid corrosion inhibitors, which typically will be provided in treatment concentrations of from about 1,000 ppm, based upon the weight of the entire treatment fluid to about 60,000 ppm of such weight. Most often, the total amount of corrosion inhibitors will range from about 1 ,000 to 30,000 ppm.
• the treatment level of the acid corrosion inhibitor will depend upon the particular physical characteristics of the well, the high alloy steel conduit, temperature and pressure considerations, the selected acidic injection medium, and the like.
• the treatment level of the acid cor- rosion inhibitor of this invention will vary depending upon a wide variety of complex, interrelated parameters including, but not limited to, the particular physical characteristics of the system or well, the nature of the steel, temperature and pressure considerations, the acid and strength thereof in the system, and the like. Nevertheless, to give a sense of the typical proportions that might be used, non-limiting effective amounts of the corrosion inhibitor ranges from about 0.1 to about 10 gpt (gallons of inhibitor per thousand gallons of acid), depending on the acid strength. (This could also be expressed as 0.1 to 10 Ipt - liters per thousand liters of acid.) The treatment level also depends upon the temperature and exposure time, with the following being non-limiting, representative examples:
• Twenty (20) gpt (20 Ipt) of corrosion inhibitor intermediate is commonly used in acid systems at or above 250°F (121 °C) in one non-limiting embodiment. Proportions of 2-4 gpt (2-4 Ipt) may be suitable in some environments (N-80 steel test coupons) at up to 270°F (132°C).
• the amount of corrosion inhibitor based on the liquid being inhibited ranges from about 0.1 to about 22 volume %, preferably from about 3 to about 6 volume%. It will be appreciated that these treatment levels will be different for other mineral acids and other halogen acids.
• the invention will be described further in the following illustrative Examples, which are non-limiting and serve only to further illuminate the invention.
• Test 1 15% HCI, 6 hrs. at 2000 psi (1.4 x 10 4 kPa) (nitrogen) or 3000 psi (2.1 x 10 4 kPa) (kerosene) 300°F (149°C).
• Test 2 15% HCI, 2 hrs. at 2000 psi (1.4 x 10 4 kPa) (nitrogen) or 3000 psi (2.1 x
• Test 3 28% HCI, 6 hrs. at 2000 psi (1.4 x 10 4 kPa) (nitrogen) or 3000 psi (2.1 x 10 -.4 * kPa) (kerosene) 250°F (121 °C).
• Test 4 28% HCI, 6 hrs. at 2000 psi (1.4 x 10 4 kPa) (nitrogen) or 3000 psi (2.1 x
• TFT is a conventional acetylenic alcohol containing inhibitor corrosion inhibitor of known performance containing about 30 vol.% methanol solvent.
• Formula A and Formula B are identical except that formula A use methanol as solvent and is offered as a comparison to formula B which is an example of the invention using formic acid solvent. It will be appreciated that the inventive corrosion inhibitor of Example 3 gives noticeably improved corrosion inhibition as contrasted with the comparative Examples 1 and 2.
• the 0.056 lb/ft 2 (0.273 kg/m 2 ) result for Test 1 of Example 3 is about five times better than the 0.222 lb/ft 2 (1.08 kg/m 2 ) of Example 1 or the 0.277 lb/ft 2 (1.35 kg/m 2 ) of Example 2. Similar comparisons can be made for the other Tests.
• the inventive corrosion inhibitor is consistently better for all Tests.
• Formula C of Inventive Example 4 was similar to Formula B of Inventive Example 3 except that a surfactant was not used. With the exception of Test 1 , the results are comparable to Example 3. It is surprising and unexpected that the addition of an acid, such as formic acid, and ester derivatives thereof, would reduce corrosion in the HCI environment of these Examples.
• Comparative Example 1 are compared in the Figure chart as a function of temperature. It should be remembered that the corrosion loss scale of the y-axis is a logarithmic scale. This data, presented below in Table II, was collected using N-80 tubing steel in 15% HCI. It may be seen that the corrosion inhibitor of Inventive Example 3 far outperforms that of Comparative Example 1.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Cosmetics (AREA)
• Fats And Perfumes (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=28457253

Family Applications (1)

Country Status (7)

Families Citing this family (18)

Family Cites Families (17)

• 2003
  • 2003-03-20 US US10/393,465 patent/US20030183808A1/en not_active Abandoned
  • 2003-03-25 EP EP03728275A patent/EP1497482A2/en not_active Ceased
  • 2003-03-25 AU AU2003233426A patent/AU2003233426A1/en not_active Abandoned
  • 2003-03-25 BR BR0303658-8A patent/BR0303658A/pt not_active Application Discontinuation
  • 2003-03-25 WO PCT/US2003/009047 patent/WO2003083173A2/en not_active Application Discontinuation
  • 2003-03-25 CA CA002482513A patent/CA2482513A1/en not_active Abandoned
  • 2003-11-07 NO NO20034955A patent/NO20034955L/no not_active Application Discontinuation
• 2006
  • 2006-04-24 US US11/409,789 patent/US7655158B2/en active Active

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events